KR800000343B1 - Manufacturing method of ethylene - Google Patents

Abstract

Ethylene was polymd. or copolymd. using catalysts contg. A) hydrocarbon-insol. reaction products of AlαMgβR'mR'n(OSiR3R4R5)l(OSiR6R7R8) p [R1,R2 = C1-10 hydrocarbon radical, R3,R4,R5,R6,R7,R8, = H or C1-12 hydrocarbon radical, α,β>1, β/α = 1-10, m,n,l,p>0,α,β= m+n+l+p=3α+2β, 0<1+p/α+β<=0.80 with Ti or V halides, and, optionally B) AlR9qx3-q [9 = C1-20hydrocarbon radical, X =H, halogen, alkoxy. aryloxy or syloxy group, q = 1-3 .

Description

Ethylene Polymerization

The present invention relates to a polymerization method of ethylene and a copolymerization method of ethylene with other olefins.

More specifically, the present invention relates to low pressure polymerization of novel ethylene by a novel catalyst synthesized using an organoaluminium-magnesium complex.

For low pressure polymerization of polyethylene using a catalyst of a transition metal compound of group IV-VIA of the periodic table and an organometallic compound of group I-III of the periodic table, K. Since the discovery of K. Ziegler, numerous catalysts have been developed and proposed.

However, most catalyst systems lack activity and require a process for removing the catalyst from the produced polymer, and the catalyst is expensive.

In recent years, the development of high activity catalysts with the aim of reducing the cost of catalysts while omitting the catalyst removal process and simplifying the production process has been actively carried out.

Catalysts called high activity catalysts are roughly classified into two types. That is, a catalyst system using a combination of a so-called supported catalyst obtained by synthesizing a Ziegler-based catalyst on a solid surface and a solid component obtained by reducing a titanium or vanadium compound from a specific organometallic compound with a specific organometallic activator. to be. As the supported catalyst, many systems using magnesium halides, hydroxy halides, alkoxides or organic acid salts as carrier components are known to exhibit particularly high activity (for example, JP 43-13050, 47-42039 and 47-42137 and JP 47-5941) In addition, certain combinations of organometallic and transition metals are used in combination with a solid component obtained by the reaction of a Greenia reagent or RMgOR 'compound synthesized in an inert medium with the transition metal compound. Catalysts (for example, Japanese Patent Application No. 47-40959, Japanese Patent Application No. 46-19274) and catalysts using solid components obtained by the reaction of a specific organic aluminum compound with a titanium compound (Japanese Patent Application No. 47-26380). ), Or catalysts using solid components containing titanium and vanadium compounds (for example, Japanese Patent Application Nos. 47-28708 and 47-28709) and the like are known as high activity catalysts.

These catalysts can satisfy the activity of the transition metal sugar, but the activity of the solid component sugar cannot be said to be sufficiently high value, and if the catalyst removal process is omitted completely, the degradation of the polymer due to the halogen residue in the polymer, etc. Is not reaching the problem.

The present inventors have conducted studies on catalysts having high activity per solid component, and have combined a specific solid component obtained by reacting an organoaluminium-magnesium complex containing a specific alkoxy or aryloxy group with a titanium or vanadium compound with an organic aluminum compound. It was found that an extremely highly active catalyst was obtained, which led to the present invention.

0.80인 관계를 가진다]로 표시되는 유기 알미늄-마그네슘 착체와, (ii) 적어도 1개의 할로겐 원자를 가지는 티탄 또는 바나듐 화합물과의 반응에 의하여 생성하는 탄화수소 불용성 반응 생성물과,That is, in the present invention, [A [(i) general formula Al _α Mg _β R ¹ _m R ² _n (OSiR ³ R ⁴ R ⁵ ) ₁ (OSiR ⁶ R ⁷ R ⁸ ) _p [wherein R ¹ and R ² are A hydrocarbon group of 1-10 carbon atoms, R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ represent hydrogen or a hydrocarbon group of 1-12 carbon atoms, α, β are one or more numbers, β / α is 1-10, and m, n, l, p are zero or more numbers α, β with m + n + l + p = 3α + 2β and 0 <l + p / α + β

Having a relationship of 0.80], a hydrocarbon insoluble reaction product produced by reaction with an organic aluminum-magnesium complex represented by (ii) a titanium or vanadium compound having at least one halogen atom,

[B] General formula AlR ⁹ _q X _3-q [wherein R ⁹ is a hydrocarbon group having 1-20 carbon atoms, X is a group selected from hydrogen, halogen, alkoxy, aryloxy or siloxy group, q is 1- Number of 3] to a method of polymerizing ethylene or other olefins with ethylene using a catalyst obtained by reacting an organoaluminum compound.

The present invention is to provide an efficient ethylene polymerization method with an extremely highly active catalyst having a novel organoaluminum magnesium complex as one component.

It is already known in the patent of K. Ziegler as a catalyst combining an organic magnesium compound with a transition metal compound (see Japanese Patent Application No. 32-1546). However, since the organic magnesium compound is insoluble in an inert hydrocarbon medium, most of the amount used is effective. Not used. In addition, it is not successful in obtaining high activity.

In order to overcome such disadvantages, a test using an organic magnesium compound was made available. (Refer to the aforementioned special missions 47-40959 and 46-19274)

The inventors also found that a hydrocarbon-soluble organoaluminum-magnesium complex and a titanium or vanadium compound having the general formula Al _n Mg _m R _{3 n} R ' _2m where R and R' are hydrocarbon groups and n and m are zero or more numbers. By combining the solid reaction product synthesized with the organic aluminum compound, a much higher activity catalyst was found and patented than when the above soluble organic magnetic compound was used.

The inventors have found that the siloxy group-containing organic aluminum-magnesium complex is soluble in hydrocarbon solvents, and the novel complex is applied to complete the novel ultra-high activity catalyst.

Generally, when alkoxy or aryloxy groups are introduced into the dialkyl magnesium compound represented by R ₂ Mg in a molar ratio of the range of the present invention, a hydrocarbon insoluble compound is formed.

Therefore, the solubility of the compound of the present invention is estimated to have changed significantly due to the complexing of organoaluminium-magnesium.

When ethylene was polymerized using a catalyst in which a hydrocarbon-insoluble reaction product synthesized using this novel siloxy group-containing organoaluminium-magnesium complex was combined with an organoaluminum compound, an organoaluminium-magnesium compound containing no siloxy group was used. Compared with the case, the polymerization activity is slightly decreased, but the molecular weight is extremely easily controlled, and a polymer excellent in the narrow structure regularity of the molecular weight distribution is obtained.

This excellent performance of the catalyst of the present invention is explained in the examples described below.

MI used in these examples represents a melt index and is measured under conditions of a temperature of 190 ° C. and a load of 2.16 kg according to ASTM and D-1238. R means the value obtained by dividing the value measured by 21.6 kg under the measurement condition of MI divided by MI, which is a measure of the molecular weight distribution, and the lower the value, the narrower the molecular weight distribution.

As is apparent from Example (1), the catalyst of the present invention has a slightly lower activity than the catalyst filed earlier, but provides a polymer having a high MI value, that is, a low molecular weight.

Therefore, in the case of producing a polymer having the same molecular weight under a constant polymerization pressure, it is possible to increase the activity again since the amount of hydrogen used is small and the partial pressure of ethylene can be relatively high.

In addition, the polymer obtained has a narrow molecular weight distribution, and thus has a sufficiently high strength even in the low molecular weight region, and is suitable for the production of large molded articles by the injection molding method.

The activity per solid component of the catalyst of the present invention is 20,000 g polymer / g solid component and ethylene pressure kg / cm ² . Times above are possible and are higher than any reported value of the catalyst known up to this point. In this connection, the values of patents (for example, the aforementioned patents) of the highly active catalysts which are already known are 10.000 or less.

The organoaluminum magnesium complex of the general formula Al _α Mg _β R ¹ _m R ² _n (OSiR ³ R ⁴ R ⁵ ) ₁ (OSiR ⁶ R ⁷ R ⁸ ) _p used in the synthesis of the catalyst of the present invention will be described. A hydrocarbon group an alkyl group of 1-10 carbon atoms represented by R ¹ in the formula. Examples are methyl, ethyl, propyl, butyl, amyl, hexyl, octyl, decyl, etc., 1-10 carbon atoms again indicated by R ² The hydrocarbon group of is an alkyl group or an aryl group and a methyl, ethyl, n-propyl, n-butyl, amyl, hexyl, octyl or phenyl group is a suitable group.

Groups represented by R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ represent hydrogen or a hydrocarbon group of 1-12 carbon atoms, and examples thereof include methyl, ethyl, propyl, butyl, hexyl, octyl and the like. Cycloalkyl groups, such as an alkyl group, a cyclohexyl, and a methylcyclohexyl group, a phenyl, a naphthyl group, etc. are preferable.

Examples of the siloxy group include, for example, methyldihydroxy, methylhydrosiloxy, trimethylsiloxy, methylethylhydrosiloxy, methyldiethylsiloxy, triethylsiloxy, methylbutylhydrosiloxy, dimethylbutylsiloxy, methylphenyl Hydrosiloxy, ethylphenylhydrosiloxy, methylethylphenylsiloxy, triphenylsiloxy, α-naphthylphenylmethylsiloxy and the like.

0.80의 관계식을 가진다.α and β are one or more numbers, and the ratio β / α of aluminum and magnesium is 1-10, preferably 2-6. m, n, o, p are zero or greater than zero, and m + n + l + p = 3α + 2β, 0 <l + p / α + β

It has a relation of 0.80.

The formula of this relationship shows the stoichiometric ratio between the valences of aluminum and magnesium atoms and the number of substituents, and the following formula indicates that the molar ratio of siloxy groups is 0.80 or less with respect to the total number of moles of metal atoms.

The complex is a reaction of an organomagnesium compound of the general formula R ₂ Mg [R is a hydrocarbon group] with siloxy aluminum or an organomagnesium of R ₂ Mg or R'MgX [R, R 'is a hydrocarbon group, X is a halogen] Hydrocarbon soluble complexes (see West German Patent Application Publication No. 2232685) synthesized by the reaction of a compound with trialkylaluminum can also be synthesized in accordance with the reaction with cyranol. It is preferable to use suitable conditions of reaction 100 degrees C or less.

The structure of the complex is not clear, but since the complex is soluble in that the R ₂ Mg compound is insoluble in a hydrocarbon solvent, a complex composed of an aluminum component and a magnesium component is formed and is assumed to be a single complex or a complex mixture. In addition, it is considered that the hydrocarbon group and siloxy group bonded to aluminum and magnesium are mutually causing an exchange reaction.

Next, as the titanium or vanadium compound [component (ii)] having at least one halogen atom as the second component, titanium tetrachloride, titanium tetrabromide, titanium tetrachloride, ethoxy titanium trichloride and propoxytitanium trichloro Titanium, such as a lide, butoxy titanium trichloride, dibutoxy titanium chloride, tributoxy titanium monochloride, vanadium tetrachloride, vanadium trichloride, monobutoxy vanadil dichloride, dibutoxy vanadil monochloride, etc. Or alone or a mixture of halides, oxyhalides, and alkoxyhalides of vanadium.

The reaction between the organoaluminum-magnesium complex and the titanium or vanadium compound is an inert reaction medium such as aliphatic hydrocarbons such as hexane and heptane, aromatic hydrocarbons such as benzene, toluene and xylene, and alicyclics such as cyclohexane and methylcyclohexane. The temperature is up to 100 ° C in the hydrocarbon, preferably 50 ° C or less.

The reaction ratio of the two catalyst components is recommended for obtaining high activity in the range of 0.05-50 mol, especially 0.2-10 mol, of the organoaluminum-magnesium complex to 1 mol of the titanium or vanadium compound. The number of moles of the organoaluminum-magnesium complex uses the sum of the gram molecular weights of the aluminum and magnesium components.

For example, AlMg ₄ (C ₂ H ₅ ) (nC ₄ H ₉ ) ₈ (OSiH.CH ₃ .C ₂ H ₅ ) ₂ has 5 mol of 788.6 g corresponding to the molecular weight of this structural formula. The hydrocarbon insoluble reaction product obtained according to the reaction may be used as it is when the reaction is completed, but in order to increase the reproducibility of the polymerization, it is preferable to separate it from the reaction solution.

In the organic aluminum compound a component [component (B)] of the present invention as the catalyst uses a compound represented by the general formula AlR ⁹ _q X _3-q alone or in mixture. The hydrocarbon group having 1 to 20 carbon atoms represented by R ⁹ includes aliphatic hydrocarbons, aromatic hydrocarbons, and alicyclic hydrocarbons.

Moreover, group represented by X is represented by hydrogen, a halogen atom, alkoxy, aryloxy, a siloxy group, q represents the number of 1-3. In particular, in order to obtain high activity, the value of q is preferably 1.7 or more. Specific examples of these compounds include triethyl aluminum, tri-n-propyl aluminum, triisopropyl aluminum, tri-n-butyl aluminum, triisobutyl aluminum, trihexyl aluminum, trioctyl aluminum, tridecyl aluminum, Tridodecyl aluminum, trihexadecyl aluminum, diethyl aluminum hydride, diisobutyl aluminum hydride, diethyl aluminum ethoxide, diisobutyl aluminum ethoxide, dioctyl aluminum butoxide, diisobutyl aluminum octyl Oxide, diethylaluminum chloride, diisobutylaluminum-chromide, diethylhydrosiloxyaluminum dimethyl, ethylmethylhydrosiloxyaluminum diethyl, ethylaluminum dichromide, butylaluminum dichromide, ethylaluminium diethoxy Ids, ethylmethylhydrosiloxy aluminum methyl groide and the like and mixtures thereof are recommended.

Highly active catalysts are obtained by combining these alkyl aluminum compounds with the above hydrocarbon insoluble solids, but especially trialkylaluminum and dialkylaluminum hydrides are good because the highest activity is achieved.

The introduction of negative groups into trialkylaluminum or dialkylaluminum hydrides tends to lower the activity, but it is possible to produce polymers that exhibit characteristic polymerization behavior and useful polymers under high activity. By introducing an alkoxy group as an example, generation of scale in the polymerization reactor is reduced and molecular weight is easily controlled.

The reaction of the catalysts [A] and [B] of the present invention may be carried out with the addition of a positive catalyst component in the polymerization system, and with the progress of the polymerization under the polymerization tank, and may be carried out before the polymerization. Moreover, it is preferable to perform reaction rate of a catalyst component in the range of 1-3,000 mmol with respect to 1 g of [A] component, and [B] component.

As the polymerization method, conventional suspension polymerization solution polymerization is possible, and the catalyst is a polymerization solvent, for example, aliphatic hydrocarbons such as hexane or heptane, aromatic hydrocarbons such as benzene, toluene or xylene, cyclohexane or methylcyclohexane, etc. Formula hydrocarbons may be introduced together into the reactor and indented ethylene at 1-50 kg / cm ² in an inert atmosphere and the polymerization may proceed at a temperature from room temperature to 150 ° C. Moreover, in order to adjust the molecular weight of a polymer, it is also possible to add hydrogen, a halogen hydrocarbon, or an organometallic compound which is easy to cause chain transfer.

It is also possible to polymerize in the presence of mono-olefins such as propylene, butene-1 and hexane-1 using the catalyst of the invention.

Examples of the present invention are shown below, and the present invention is not limited according to the embodiments thereof. In addition, MI and R in an Example have the same meaning as the above-mentioned, and a catalyst efficiency is represented by the polymer production amount g per 1 g of solid components, 1 hour, and ethylene pressure kg / cm <^2> .

Example 1

(1) Synthesis of Organoaluminum-Magnesium Complex

6.81 g of di-n-butylmagnesium and 6.81 g of an organoaluminum compound having composition Al (C ₂ H ₅ ) _{1 .50} (OSiH.CH ₃ .C ₂ H ₅ ) ₁ .50 together with 200 ml of n-heptane Into a 500 ml glass flask and reacted at 80 ° C. for 2 hours, the composition AlMg _{3 · 0} (C ₂ H ₅ ) _{1 · 50} (nC ₄ H ₉ ) _{6 · 0} (OSi · H · CH ₃ ㆍ C ₂ H ₅ ) A _{1 · 50} organic aluminum-magnesium complex is synthesized. 80 ml of the n-heptane solution containing 40 mmol of this complex and 80 ml of the n-heptane solution containing 40 mmol of titanium tetrachloride were flattened in a flask having a capacity of 300 ml from which water and oxygen were removed by dry nitrogen replacement, and stirred. The reaction was carried out at -20 ° C for 2 hours and at 10 ° C for 2 hours. The resulting hydrocarbon insoluble solid is isolated, washed with n-heptane and dried under vacuum to yield 11.5 g of solid.

5 mg of this hydrocarbon-insoluble solid and 1.5 l mol of triisobutyl aluminum were degassed together with 3 liters of n-heptane degassed and vacuum degassed and placed in a 5 liter autoclave replaced with nitrogen to maintain a temperature of 85 ° C. and hydrogen 2.0 kg / cm. ^It is press-fitted at the gauge pressure of ² , ethylene is added continuously, and a voltage is made into the gauge pressure of 6.0 kg / cm <^2> . As the ethylene was replenished, polymerization was carried out for 1 hour while maintaining the voltage at a gauge pressure of 6.0 kg / cm ² to obtain 530 g of polymer. MI is 3.25, R is 32, catalyst efficiency is 26,500 g / g, solid component, time, and ethylene kg / cm ² .

Example 2

Furthermore, 41.4 g of n-butylmagnesium, 17.6 g of composition Al (C ₂ H ₅ ) ₁ ( _{0 0} (OSi.H.CH ₃ .C ₂ H ₅ ) ₂ .0 organic aluminum compound and 1,000 ml of n-heptane together with 1,000 ml Into a flask of ml and reacted at 80 ° C. for 2 hours, the composition AlMg _{4 · 0} (C ₂ H ₅ ) _{1 · 0} (nC ₄ H ₉ ) _{8 · 0} (OSi · H · CH ₃ ㆍ C _{2 ·} H ₅ ) Synthesize _{2 ·} organic aluminum-magnesium complex.

80 ml of n-heptane solution containing 40 mmol of this complex and 80 ml of n-heptane solution containing 40 m mol of Ti tetrachloride and n-butoxy titanium chromide in a 2: 1 mixture (based on Ti atoms) were dried. Nitrogen-substituted to a capacity 300ml flakes to remove moisture and oxygen, and reacted for 4 hours at 0 ℃ under stirring.

The resulting hydrocarbon insoluble solid was isolated, washed with n-heptane and dried in vacuo to give 12.6 g of solid. 5 mg of this hydrocarbon-insoluble solid and 1.5 m mol of tri n-butylaluminum are degassed together with 3 L of n-heptane dehydrated and placed in a 5 L autoclave nitrogen-substituted. The internal temperature of the haute crab is maintained at 85 ° C., hydrogen is pressurized to a gauge pressure of 2.0 kg / cm ² , and ethylene is subsequently added to bring the voltage to a gauge pressure of 6.0 kg / cm ² . As ethylene was replenished, polymerization was carried out for 1 hour while maintaining the voltage at a gauge pressure of 6.0 kg / cm ² to obtain 345 g of a polymer. MI is 5.20, R is 28, catalytic efficiency is 17,300 g / g solid component. time. Ethylene kg / cm ² .

Example 3-6

The magnesium complex and Table 1 - composition _{AlMg 4 · 0 (C 2 H} 5) 1 · 0 (nC 4 H 9) 8 · 0 (OSi and H and CH _{3 and} C ₂ H _{5) 2, 0} organic aluminum Polymerization conditions similar to those of Example (1) using 5 mg of a hydrocarbon-insoluble solid obtained by reacting the indicated titanium or vanadium compound by the same method as in Example (1) and the alkyl aluminum compound shown in the table It superposed | polymerized under the result and obtained the result as shown in Table 1.

TABLE 1

Example 7

Di-n- butyl magnesium 13.80g, composition _{Al (C 2 H 5) 1} · 0 (OSi and H and CH ₃ and C ₂ H _{5) 2 · 0} aluminum organic compound and 3.41g of 500ml with 200ml of n- hepdan Into the flask _and adjusted by reaction at 80 ° C. for 2 hours AlMg _{6 · 0} (C ₂ H ₅ ) _{1 · 0} (nC ₄ H ₉ ) _{12 · 0} (OSi · H · CH ₃ -C ₂ H ₅ ) _{2 · 0} organoaluminum-magnesium complex is synthesized. 80 ml of the n-heptane solution containing 40 mmol of this complex and 80 ml of the n-heptane solution containing 40 mmol of titanium tetrachloride were leveled and dried by a nitrogen-containing flask having a volume of 300 ml from which moisture and oxygen were removed. The reaction is carried out at 10 ° C. for 2 hours and at 5 ° C. for 2 hours. The resulting hydrocarbon insoluble solid was isolated, washed with n-heptane and dried in vacuo to give 10.8 g of solid.

₅ ml of this hydrocarbon-insoluble solid and 3 liters of n-heptane dehydrated with 3.0 mmol of the aluminum compound of composition Al (C ₂ H ₅ ) ₂ .5 (OC ₂ H ₅ ) Into the autoclave.

The internal temperature of the autoclave is maintained at 85 ° C., hydrogen is pressurized to 2.0 kg / cm ² of papermaking pressure, and ethylene is subsequently added to bring the voltage to 6.0 kg / cm ² of gauge pressure. As ethylene was replenished, polymerization was carried out for 1 hour while maintaining the voltage at a gauge pressure of 6.0 kg / cm ² to obtain 560 g of a polymer.

MI is 4.21, R is 31, catalytic efficiency is 28,000g / g solid component. time. Ethylene kg / cm ² .

Claims (1)

[A] (i) General Formula Al _α Mg _β R ¹ _m R ² _n (OSiR ³ R ⁴ R ⁵ ) ₁ (OSiR ⁶ R ⁷ R ⁸ ) _p [wherein R ¹ and R ² are 1-10 carbon atoms Of the hydrocarbon groups, R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ represent hydrogen or a hydrocarbon group of 1-12 carbon atoms, α, β is one or more numbers and β / α is 1-10 M, n, l, p are zero or more numbers, and m + n + l + p = 3α + 2β and 0 <1 + p / α + β with α, β

Having a relationship of 0.80], a hydrocarbon-insoluble reaction product formed by reaction with an organoaluminium-magnesium complex represented by (ii) a titanium or vanadium compound having at least one halogen atom, and [B] general formula AlR ⁹ _q X _{3-q wherein} R ⁹ is a hydrocarbon group of 1-20 carbon atoms, X is a group selected from hydrogen, halogen, alkoxy, aryloxy or siloxy and q is a number from 1-3 A method of polymerizing ethylene or ethylene and other olefins using a catalyst obtained by reacting an organoaluminum compound.